Reforming catalyst comprising low valence Ti, V or Cr composited with non-oxidizing high surface area support

ABSTRACT

This invention relates to a novel catalyst for reforming gasoline comprising a low valence titanium, vanadium and/or chromium metallic component composited with a non-oxidizing high surface area support. The low valence metallic component is present in divalent form or as a combination of the metallic state and the divalent form - preferably as a chloride and/or bromide. The preferred support is a high surface area coke.

The present invention is a continuation-in-part of Ser. No. 335,447,filed Dec. 29, 1981 now U.S. Pat. No. 4,394,252.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a catalyst for reforming gasoline to raise theoctane number thereof commprising a low valence titanium, vanadiumand/or chromium metallic component composited with a non-oxidizing highsurface area support. The low valence metallic component is present indivalent form or as a combination of the metallic state and the divalentform--preferably a chloride and/or bromide and the support is preferablya high surface area coke.

2. Description of the Prior Art

Vanadium, titanium and chromium have previously been used as a catalyticcomponent in hydrocarbon conversion processes.

In U.S. Pat. No. 3,282,828, colloidally dispersed unsupported vanadiumhalides which may be divalent form are disclosed as suitable slurrycatalysts in the hydrorefining or decontaminating of petroleum crude oiland other heavy hydrocarbon fractions.

However, as taught in U.S. Pat. No. 3,282,828, the use ofvanadium-containing catalyst in fixed-bed catalytic processes orfixed-fluidized bed processes has been virtually precluded due to thedifficulty of maintaining such catalyst in active condition. Likewise,moving-bed processes utilizing supported vanadium also have not beensatisfactory.

N.S. Koslov et al in an article published in NEFTE KHIMIYA (PetroleumChemistry), Vol. 19, No. 3, P. 37D (1979) entitled: THE EFFECT OFCHROMIUM ON THE ACTIVITY OF PLATINUM-ALUMINA CATALYST IN DEHYDROGENATIONAND DEHYDROCYCLIZATION REACTIONS disclosed that addition of chromium toPt--Al₂ O₃ catalysts, reduced cracking side reactions and increasedconversion and selectivity for n-heptane dehydrocyclization reactions.Koslov et al disclose that for the dehydrocyclization of n-heptane withtheir Pt-Cr-Al₂ O₃ catalyst, coke increases with Cr content but goesthrough a maximum and then decreases. AT 3% Cr the coke make is lessthan for a Pt-Al₂ O₃ catalyst without Cr. The authors attribute theforegoing characteristics of chromium promoted Pt-Al₂ O₃ catalysts to beincreased dispersion and decreased particle size of platinum observedwhere the Pt is promoted with Cr within a given range.

In the present invention, it has been discovered that the reforming ofgasoline can be effected utilizing a vanadium, titanium orchormium-containing catalyst which possesses and retains activity inboth fixed-bed and moving-bed processes. The catalyst of the presentinvention comprises a combination of (a) one or more of the metalliccomponents V, Ti and Cr in their lower valent states; the metalliccomponents can be present in the +2 valence state or in the form of boththe metal and +2 valence state metal such that the "average valence" inthe catalyst may vary from about +1 up to +2; and, (b) a high surfacearea support for the metallic component(s) which is characterized bysurface area maintenance at reaction and/or activation conditions andmost importantly by the property of not oxidizing the metalliccomponents to the +3 or higher valence states over the temperature rangeto which said catalyst is subjected. As will be explained more fullyhereafter, this excludes the use of refractory oxides, such as the Al₂O₃ support of Koslov et al, which it has been found can under someconditions oxidize lower-valence salts such as metallic or divalentvanadium to higher oxidation states. A suitable support is a non-oxygencontaining high surface area material such as high surface area coke.

SUMMARY OF THE INVENTION

This invention relates to a catalyst for reforming gasoline to raise theoctane number thereof comprising a low valence titanium, vanadium and/orchromium metallic component composited with a non-oxidizing high surfacearea support. The low valence metallic component is present in divalentform--preferably a chloride and/or bromide. The support is preferably ahigh surface area coke.

The object of this invention is to provide a non-noble metal-containingcatalyst for upgrading low octane gasoline fuel. Although othercatalytic components, to the extent that they do not oxidize thecatalytic component of the reforming catalyst, can also be present, thegreatest economic advantage of the invention is attained where noblemetals are not used in the refining catalyst. The reforming of gasolineto increase octane number involves basically three reactions:

1. Dehydrogenation of cyclohexanes to benzenes.

2. Dehydrogenation and rearrangement of alkylcyclopentanes to benzenes.

3. Cyclisation and dehydrogenation of straight chain heptanes, octanesand nonanes to benzenes.

Suitably such a process is carried out at high temperatures (400°-500°C.) and low H₂ pressures (5-50 Bar) with Pt--PtCl₂ or Pt--PtBr₂ onalumina or silica-alumina supports. The supply of platinum is limited,its price is high, its use is expanding and the reliability of its majorsource, the Republic of South Africa, is uncertain.

In its broadest aspect the method of the invention relates to a methodof reforming a hydrocarbonaceous feedstock in the presence of areforming catalyst the improvement utilizing a catalyst comprising acatalytic component of titanium, vanadium, chromium or mixtures of suchelements, in the divalent state or both the divalent and metal statesuch that the "average valence" is from about +1 up to +2, compositedwith a high surface area supported which will not oxidize such catalyticcomponents to an elevated valence state at reforming conditions, thatis, a valence state of +3 or higher.

The catalyst of the invention comprises a catalytic component selectedfrom the group consisting of titanium, vanadium and chromium andmixtures thereof. The catalytic component is present in divalent form orin both metal and divalent form with the ratio of divalent form to metalbeing about 1:1 or grater; suitably a ratio wherein the major portion ofthe metal is present in divalent form. The catalytic component isassociated with a high surface area support which will not oxidize suchcatalytic component at the conditions of use.

Preferably the catalytic component is present as a chloride or bromideor as a mixture of chlorides and bromides.

The high surface area support is preferably coke, suitably prepared bylow temperature tar formation from brown coals, lignite, peat or coal.Such coke have high surface areas of from about 200 to about 500 M² /g,suitably above about 250 M² /g and are readily available.

The catalytic component of the reforming catalyst may be present inamounts which vary from about 2% to about 15% by weight based on theweight ratio of metal in the catalytic component to high surface areasupport and preferably from about 5% to about 10% by weight.

The method of achieving the low valence required for the metalliccomponent; that is, the divalent form or combination of metallic anddivalent form, is by heating the support impregnated with two valentmetal ions in a reducing atmosphere (a hydrogen atmosphere is suitable)at a temperature of from about 400° to 800° C. The lower the temperatureselected, the longer the exposure to the H₂ atmosphere required. Forinstance, at a temperature of about 700° C., continuous contact with aH₂ atmosphere yields satisfactory results, whereas, at a temperature of500° C., an exposure of about 8 hours is provided.

The method developed for preparing the reforming catalyst comprisesimpregnating the selected high surface area support at non-oxidizingconditions with a solution of the catalytic component in divalent form;and, heating the impregnated support at a temperature of from about 400°C. to about 800° C. in a reducing atmosphere to form the desiredcatalyst wherein the catalytic component is present in divalent form orin an admixture of the divalent form and the metal, the ratio of thecatalytic component present as the metal being at least 1:1.

EXAMPLE

100 g of a high surface area coke --450 m² /g--10-30 mesh, prepared bylow temperature tar formation from peat--German Torf Institute, or frombrown coal by Rheinische Braun Kohlenwerke A.G., West Germany, or fromlignite by Neyvdi Lignite Co., Ltd., India--is impregnated with 100 ml NHCl containing 20 g VCL₂ in an N₂ atmosphere. After evaporating the HCland drying, the coke contains 8.35% V. When carrying out the sameprocedure with CrCl₂ and TiCl₂, the coke will contain 8.5% Cr and 8.05%Ti respectively.

Practically the same amount of metal ion is impregnated as the dibromideif 35 g of the corresponding dibromides are dissolved in 100 ml 1 N HBrand this solution adsorbed on the high surface coke under an N₂atmosphere. The two valent metal halides are available commercially. Butsolutions of two valent metal ions in HCl or HBr can most economicallybe obtained by electrochemically reducing, at a voltage of 2.5, highervalent metal ions, like TlCl₃, CrCl₃, VO₂ Cl₂, dissolved in 1 N HCl orthe corresponding bromides in 1 N HBr. VO₂ Cl₂ is conveniently obtainedby refluxing V₂ O₅ in 20% HCl.

A 50 cm section of a pipe with a 2 cm diameter serving as a reactor isfilled with 100 ml catalyst, consisting of 20% VCl₂ on coke, under anitrogen blanket. The nitrogen is displaced by hydrogen and the reactorheated to 700° C. for one hour, while the catalyst bed is swept byhydrogen. This will reduce the ratio of halide to metal ion from 2.0 tol.8. The temperature is then reduced to 450° C.

Preheated to 450° C. n-heptane vapors, together with hydrogen at 10 Barpressure, are passed through the catalyst bed at 450° C. and thencondensed.

At 1/2 LHSV--liquid hourly space velocity--50% of the heptane isconverted to toluene, meaning that 25 ml n-heptane are converted to 20ml toluene at that rate. Passing a Midcontinent naphtha through thecatalyst bed at a catalyst temperature of 470° C., a pressure of 10 Bar,a LHSV of 2.5 and a H₂ /feed mol ratio of 4, the following results areobtained:

    ______________________________________                                                       Charge                                                                        Midcontinent                                                                           86 Percent                                                           Naphtha  Yield                                                 ______________________________________                                        Spec gr. at 15° C.                                                                      0.7641     0.7811                                            I.B.P. °C. 75        51                                                10% 110                     80                                                50% 140                     129                                               90% 170                     170                                               E.P. 195                    190                                               Paraffins %      48         34.6                                              Naphthenes %     45         10.2                                              Aromatics %       7         41.2                                              C.sub.1 to C.sub.4          14                                                R.O.N. + 3 ml TEL                                                                              51         94.5                                              ______________________________________                                    

These results compare favorably with results obtained with noble metalcatalysts.

Thus, a new method and catalyst for reforming feedstocks utilizing alow-valence vanadium, chormium and/or titanium catalytic componentcomposited on a non-oxidizing high surface area support is disclosed.Although a specific example of the invention has herein above beendescribed it will be obvious to those skilled in the art, that variousmodifications may be made without departing from the spirit of theinvention which is intended to be limited solely by the appended claims.

I claim:
 1. A reforming catalyst comprising:(a) a catalytic componentselected from the group consisting of titanium, vanadium and chromiumand mixtures thereof, said catalytic component being present in divalentform or in an admixture of the divalent form and the metal, the ratio ofthe catalytic component in divalent form to the catalytic componentpresent as the metal being at least 1:1; and (b) a non-refractory oxide,high surface area support for said catalytic component which will notoxidize said catalytic component at reforming conditions.
 2. Thecatalyst of claim 1 further characterized in that the catalyticcomponent is present in the form of a chloride, bromide or a mixture ofchlorides and bromides.
 3. The catalyst of claim 2 further characterizedin that the catalytic component comprises vanadium.
 4. The catalyst ofclaim 2 further characterized in that the catalytic component compriseschromium.
 5. The catalyst of claim 2 further characterized in that thecatalytic component comprises titanium.
 6. The catalyst of claim 2further characterized in that the high surface area support comprisescoke.
 7. The catalyst of claim 3 further characterized in that the highsurface area support comprises coke.
 8. The catalyst of claim 4 furthercharacterized in that the high surface area support comprises coke. 9.The catalyst of claim 5 further characterized in that the high surfacearea support comprises coke.
 10. The catalyst of claim 1 furthercharacterized in that the high surface area support comprises coke. 11.The catalyst of claim 6 where said high surface area coke has a surfacearea of from about 200 to about 500 M² /g.
 12. The catalyst of claim 7wherein said high surface area coke has a surface area of from about 200to about 500 M² /g.
 13. The catalyst of claim 8 wherein said highsurface area coke has a surface area of from about 200 to about 500 M²/g.
 14. The catalyst of claim 9 wherein said high surface area coke hasa surface area of from about 200 to about 500 M² /g.
 15. The catalyst ofclaim 10 wherein said high surface area coke has a surface area of fromabout 200 to about 500 M² /g.
 16. The catalyst of claim 11 furthercharacterized in that the catalytic component of the reforming catalystis present in an amount of from about 5% to about 10% by weight based onthe weight ratio of metal in the catalytic component to coke.
 17. Thecatalyst of claim 11 further characterized in that the catalyticcomponent of the reforming catalyst is present in an amount of fromabout 5% to about 10% by weight based on the weight ratio of metal inthe catalytic component to coke.
 18. The catalyst of claim 12 furthercharacterized in that the catalytic component of the reforming catalystis present in an amount of from about 5% to about 10% by weight based onthe weight ratio of metal in the catalytic component to coke.
 19. Thecatalyst of claim 13 further characterized in that the catalyticcomponent of the reforming catalyst is present in an amount of fromabout 5% to about 10% by weight based on the weight ratio of metal inthe catalytic component to coke.
 20. The catalyst of claim 4 furthercharacterized in that the catalytic component of the reforming catalystis present in an amount of from about 5% to about 10% by weight based onthe weight ratio of metal in the catalytic component to coke.
 21. Thecatalyst of claim 15 further characterized in that the catalyticcomponent of the reforming catalyst is present in an amount of fromabout 5% to about 10% by weight based on the weight ratio of metal inthe catalytic component to coke.
 22. A method of preparing a reformingcatalyst comprising a catalytic component selected from the groupconsisting of titanium, vanadium and chromium and mixtures thereof, saidcatalytic component being present in divalent form and the metal, theratio of the catalytic component in divalent form to the catalyticcomponent present as the metal being at least 1:1, composited with ahigh surface area support which will not oxidize said catalyticcomponent at reforming conditions which method comprises:(a)impregnating the high surface area support at non-oxidizing conditionswith a solution of the catalytic component in divalent form; and (b)heating the impregnated support at a temperature of from about 400° C.to about 800° C. in a reducing atmosphere to form a catalyst wherein thecatalytic component is present in divalent form or in an admixture ofthe divalent form and the metal, the ratio of the catalytic componentpresent as the metal being at least 1:1.
 23. The method of claim 22further characterized in that the impregnating solution comprisesdivalent titanium, vanadium or chromium chloride or bromide or a mixtureof divalent titanium, vanadium or chromium chlorides or bromides. 24.The method of claim 23 further characterized in that the impregnationsolution comprises vanadium dichloride, vanadium dibromide or a mixturethereof.
 25. The method of claim 22 further characterized in that thereducing atmosphere comprises hydrogen.
 26. The method of claim 23further characterized in that the reducing atmosphere compriseshydrogen.
 27. The method of claim 24 further characterized in that thereducing atmosphere comprises hydrogen.